Azo dyes from sulfonated 3-sulfonated 3-amino-2,1-benzisothiazoles with 1,2,3,4-tetrahydroquinoline or 2,3-dihydro-1,4-benzoxazine couplers

ABSTRACT

Disclosed are azo dyes in which the diazo component is a diazotized 3-amino-2,1-benzisothiazole compound bearing one or two sulfo groups, and the coupler is either a 1,2,3,4-tetrahydroquinoline or a 2,3-dihydro-1,4-benzoxazine compound. These dyes exhibit excellent dyeing and fastness properties on polyamide fibers and also impart color to cellulose acetate fibers and wool. The dyes correspond to the general formula: ##STR1## wherein R 5  is 0-3 substituents independently selected from halogen, cyano, alkyl, alkoxy, sulfo, and the like; M is H + , Na + , K +   or the like; and C is the coupler which may be substituted with groups known to the art.

This invention relates to azo dyes in which the diazo component is froma 3-amino-2,1-benzisothiazole compound bearing one or two sulfo groups,and the coupler is a 1,2,3,4-tetrahydroquinoline or2,3-dihydro-1,4-benzoxazine compound. These dyes, in general, exhibitexcellent dyeing and fastness properties on polyamide fibers, impartingneutral to greenish blue shades thereto, and also impart color tocellulose acetate fibers and wool, and are particularly valuable in notflaring red under artificial light while retaining good lightfastness.

The dyes correspond to the general formula: ##STR2## wherein R⁵ is 0-3substituents independently selected from halogen, cyano, alkyl, alkoxy,alkylthio, alkylsulfonyl, sulfamoyl, alkylsulfamoyl, alkanoyloxy,carbamoyl, alkylcarbamoyl, alkoxycarbonyl, acylamido, and SO₃ M; M isselected from H⁺, NH₄ ⁺, Na⁺, K⁺, and the colorless cations of salts ofprimary, secondary, and tertiary aliphatic and aryl amines; C is acoupler having the formula ##STR3## wherein R is selected from hydrogen,alkyl, aryl, and cycloalkyl; R¹, R², and R³ are each selected fromhydrogen and alkyl; R⁴ is 0-2 substituents and R⁶ is 0 or 1 substituentselected from alkyl, alkoxy, halogen, acylamido, alkylthio, and aryloxy;and wherein the alkyl moieties of R, R⁴, R⁵ and R⁶, e.g. of the alkoxygroups, are unsubstituted or substituted with 1-3 substituentsindependently selected from halogen, CN, OH, alkoxy, aryloxy,alkoxyalkoxy, alkanoyl, alkanoyloxy, carbamoyl, alkylcarbamoyl,sulfamoyl, alkylsulfamoyl, aryl, alkoxycarbonyl, alkoxyalkanoyloxy, andcycloalkyl.

Typical of the amines which may be used to form the "M" salts aretriethylamine, tri(2-hydroxyethyl)amine, di(2-hydroxyethyl)amine, andN,N-dimethylaniline.

Preferred of the present dyes are those wherein: R⁵ is 0-3 substituentsindependently selected from Cl, Br, alkyl, alkoxy, and --SO₃ M; R isalkyl, or alkyl substituted with 1-3 substituents independently selectedfrom hydroxy, Cl, Br, alkoxy, carbamoyl, alkanoyloxy, alkoxycarbonyl,cyano, phenyl, and sulfamoyl; R¹, R² and R³ are each independentlyselected from H and methyl; and R⁴ is 0-2 substituents independentlyselected from alkyl, alkoxy, alkylthio, phenyl, and acylamido. The mostpreferred of the above dyes are those wherein R⁵ is H or one of saidpreferred substituents in the 4 or 5 position, and R⁴ is H or one ofsaid preferred substituents in the seven position.

The alkyl and alkylene moieties within the definitions of the above R-R⁶groups contain from 1-6 carbons and are straight or branched chain, andthe aryl groups have 6-10 ring carbons.

The dyes of this invention impart blue to greenish blue shades tofibers, particularly polyamides, and are especially useful for dyeingpolyamide (nylon) carpets, giving improvements over such dyes as shown,for example, in German Offenlegungsschrift Nos. 2,716,033 and 2,805,304,in one or more properties such as fastness to light, ozone, oxides ofnitrogen, perspiration, washing, sublimation, and crocking, leveling,migration, transfer, exhaustion, build, barre coverage, pH stability,and insensitivity to pesticides such as those containing organicphosphate esters.

This invention will be exemplified further by the following examples,although it will be understood that these examples are included merelyfor the purpose of illustration and are not intended to limit the scopeof the invention. The diazo and coupler components of the present dyescan be prepared by procedures well-known in the art.

EXAMPLE 1

A solution of 10.0 g. of 3-amino-2,1-benzisothiazole in 100 g. ofconcentrated H₂ SO₄ was heated at 50°-55° C. for one-half hour, thencooled and added to 500 ml. of cold acetone. The product was removed byfiltration and then reprecipitated from bicarbonate solution by additionof sufficient acetic acid to give a pH of 4.75-4.80. 8.5 Grams ofpurified 3-amino-2,1-benzisothiazole-7-sulfonic acid product wasobtained.

A 0.025 mol. portion (5.76 g.) of the above sulfonic acid product wasdissolved in 50 ml. of aqueous KOH (1.2 g. KOH), 50 g. of ice added, andthen 6.9 g. of NaNO₂ added, followed by dropwise addition of 10 ml. of37% HCl. The temperature was then maintained at 0° to 5° C. for one hourand the excess nitrite then destroyed with sulfamic acid.

A 0.025 mol. portion of the coupler1-(2-hydroxyethyl)-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline (5.84g.) was dissolved in 75 ml. of 6% HCl, the solution chilled in an icebath and the above diazonium solution added thereto. Sodium acetate wasadded after 30 min. to obtain a pH of 4-5 and the product was removed byfiltration after an additional one hour in the ice bath. Dilute NaClsolution (10%) was used to wash the precipitate. The dried dye weighed10.85 g. and its formula is that of the first dye of Table I.

EXAMPLE 2

Fifteen g. of 3-amino-5-chloro-2,1-benzisothiazole were added to 90 g.of 20% oleum, with external cooling to prevent the temperature fromexceeding 60° C. After one-half hour at 60° C. the solution was cooledand added to 520 ml. of cold acetone. A 7.9 g. portion of pure sulfonicacid product was removed by filtration of the chilled acetone mixture,and an additional 5.2 g. of product, only slightly less pure, wererecovered by evaporating a major part of the acetone and drowning theremaining solution in water.

The 3-amino-5-chloro-2,1-benzisothiazole-7-sulfonic acid was diazotizedin a nitrosyl sulfuric acid solution prepared from 2.16 g. of NaNO₂ in15 ml. of concentrated H₂ SO₄ below 70° C. At below 25° C., 15 ml. of1:5 acid (propionic:acetic) were added to the above solution followed by0.03 mol (7.94 g.) of the amine at 0° C., followed by 15 ml. more of 1:5acid. The temperature was held at 0° to -2° C. for two hours beforetreatment with sulfamic acid to destroy excess nitrite.

A 0.03 mol. portion of the coupler1-ethyl-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline (6.52 g.) wasdissolved in 150 ml. of 15% H₂ SO₄, the solution chilled in an ice bathand the above diazonium solution added thereto. Sodium hydroxidesolution (25%) and ice were then added until a pH of 4.15 was reached.After one hour, the dye was removed by filtration, extracted with waterat 65°-70° C., and NaCl added with cooling to get the final precipitatewhich was washed with 2% NaCl solution and dried to constant weight. Ayield of 9.09 g. of dye product was obtained. The following tables giveadditional examples of the present dyes which are prepared as above.

                                      TABLE I                                     __________________________________________________________________________     ##STR4##                                                                     Num-                                                                          ber  R.sup.5    R              R.sup.1                                                                             R.sup.2 R.sup.3                                                                    R.sup.4   M                         __________________________________________________________________________     1 H            CH.sub.2 CH.sub.2 OH                                                                         CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3                                                                              H.sup.+                    2 H            C.sub.2 H.sub.5                                                                              CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3                                                                              H.sup.+                    3 H            C.sub.4 H.sub.9 (n)                                                                          CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3                                                                              H.sup.+                    4 5-SO.sub.3 H H              CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3 CONH                                                                         H.sup.+                    5 H            C.sub.6 H.sub.5                                                                              CH.sub.3                                                                            H H  5-CH.sub.3                                                                              H.sup.+                    6 5-CN         CH.sub.2 CH.sub.2 OH                                                                         CH.sub.3                                                                            H H  5-OC.sub.2 H.sub.5                                                                      H.sup.+                    7 H            CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  H         H.sup.+                    8 H            CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 (n)                                                       CH.sub.3                                                                            H H  8-Cl      H.sup.+                    9 5-SC.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                              H     H H  7-CH.sub.3 COHN                                                                         Na.sup.+                  10 H            CH.sub.2 CH.sub.2 CONH.sub.2                                                                 CH.sub.3                                                                            H H  7-CH.sub.3                                                                              Na.sup.+                  11 5-SO.sub.2 Na                                                                              CH.sub.2 CH.sub.2 CONHC.sub.2 H.sub.5                                                        CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-Br      Na.sup.+                  12 4-CN, 5-Cl   C.sub.6 H.sub.11                                                                             CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  5,7-di-CH.sub.3                                                                         K.sup.+                   13 4,5-di-Cl6-CH.sub.3                                                                        CH.sub.2 CH.sub.2 OH                                                                         CH.sub.3                                                                            CH.sub.3 CH.sub. 3                                                                 5,7-di-CH.sub.3                                                                         K.sup.+                   14 H            CH.sub.2 OC.sub.6 H.sub.5                                                                    CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-SCH.sub.3                                                                             K.sup.+                   15 5-SO.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3                                      CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3 CONH                                                                         K.sup.+                   16 H            CH.sub.2 COCH.sub.3                                                                          CH.sub.3                                                                            H H  7-CH.sub.3 CH.sub.2 CONH                                                                K.sup.+                   17 6-SO.sub.2 NH.sub.2                                                                        CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.3                                                                            H H  7-CH.sub.3                                                                              NH.sub.4.sup.+            18 H            (CH.sub.2).sub.3 OH                                                                          CH.sub.3                                                                            H H  7-OC.sub.6 H.sub.5                                                                      NH.sub.4.sup.+            19 5-SO.sub.3 HN(Et).sub.3                                                                    CH.sub.3 CONH  CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-C.sub.6 H.sub.5 CONH                                                                  N.sup.+ H(Et).sub.3       20 H            C.sub.2 H.sub.5                                                                              CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3 SO.sub.2 NH                                                                  N.sup.+ H(Et).sub.3       21 5-CONH.sub.2 CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3 CONH                                                                         NH.sub.4.sup.+            22 H            CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 (n)                                                       CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3 CONH                                                                         N.sup.+ H(Et).sub.3       23 H            C.sub.2 H.sub.5                                                                              CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-HCONH   N.sup.+ H(Et).sub.3       24 5-Cl         CH.sub.2 CH.sub.2 COOCH.sub.3                                                                CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3                                                                              N.sup.+ H(Et).sub.3       25 5-Cl         CH.sub.2 CH.sub.2 CONH.sub.2                                                                 CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3                                                                              N.sup.+ H(CH.sub.2                                                            CH.sub.2 OH).sub.3        26 5-Cl         CH.sub.2 CH.sub.2 CN                                                                         CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3                                                                              N.sup.+ H(CH.sub.2                                                            CH.sub.2 OH).sub.3        27 4-OOCCH.sub.3                                                                              C.sub.4 H.sub.9 (n)                                                                          CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3                                                                              N.sup.+ H(CH.sub.2                                                            CH.sub.2 OH).sub.3        28 5-CH.sub.2 CONHCH.sub.3                                                                    CH.sub.2 C.sub.6 H.sub.5                                                                     CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-C.sub.6 H.sub.5                                                                       N.sup.+ H(CH.sub.2                                                            CH.sub.2 OH).sub.3        29 H            CH.sub.2 CONHCH.sub.3                                                                        CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-C.sub.6 H.sub.5 CH.sub.2                                                              N.sup.+ H.sub.2                                                               (CH.sub.2 CH.sub.2                                                            OH).sub.2                 30 5-Br         CH.sub.2 SO.sub.2 NHCH.sub. 3                                                                CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3                                                                              N.sup.+ H.sub.2                                                               (CH.sub.2 CH.sub.2                                                            OH).sub.2                 31 5-CH.sub.2 SO.sub.2 NHCH.sub.3                                                             (CH.sub.3).sub.2 CH                                                                          CH.sub.3                                                                            H H  7-CH.sub.3                                                                              N.sup.+ H.sub.2                                                               (CH.sub.2 CH.sub.2                                                            OH).sub.2                 32 5-Br         (CH.sub.3).sub.2 CHCH.sub.2                                                                  CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3 CONH                                                                         N.sup.+ H.sub.2                                                               (CH.sub.2 CH.sub.2                                                            OH).sub.2                 33 4-CHCOCH.sub.3                                                                             CH.sub.2 CH.sub.2 CONH.sub.2                                                                 CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3                                                                              N.sup.+ H(CH.sub.3).su                                                        b.2 C.sub.6 H.sub.5       34 4,5,6-tri-Cl C.sub.2 H.sub.5                                                                              CH.sub.3                                                                            H H  7-CH.sub.3                                                                              N.sup.+ H(CH.sub.3).su                                                        b.2 C.sub.6 H.sub.5       35 H            CH.sub.2 CH.sub.2 SO.sub.2 NH.sub.2                                                          CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3 CH.sub.2 CONH                                                                N.sup.+ H(CH.sub.3).su                                                        b.2 C.sub.6 H.sub.5       36 5-Me         CH.sub.2 OOCCH.sub.2 CH.sub.2 OCH.sub.3                                                      CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3                                                                              NH.sub.4.sup.+            37 5-Me         CH.sub.2 CH.sub.2 CONH.sub.2                                                                 CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3 CONH                                                                         NH.sub.4.sup.+            38 5-SO.sub.3 NH.sub.4                                                                        CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                           CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-C.sub.6 H.sub.5                                                                       NH.sub.4.sup.+            39 4-MeO        CH.sub.2 C.sub.6 H.sub.11                                                                    CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3                                                                              NH.sub.4.sup.+            40 4-MeO        CH.sub.2 CH.sub.2 OH                                                                         CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3       H.sup.+            41 4-MeO        CH(OH)CH.sub.2 CH.sub.2 OH                                                                   CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3 CONH  H.sup.+            42 5-SO.sub.3 H C.sub.2 H.sub.5                                                                              CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3       H.sup.+            43 5-SO.sub.3 H CH.sub.2 CH.sub.2 OH                                                                         CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-OCH.sub.3      H.sup.+            44 5-SO.sub.3 H CH.sub.2 CH.sub.2 OH                                                                         CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  H                H.sup.+            45 5-NHSO.sub.2 CH.sub.3                                                                      CH.sub.2 CH.sub.2 Br                                                                         CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3 CH.sub.2 CONH                                                                       H.sup.+            46 H            CH.sub.2 CH.sub.2 I                                                                          CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-HCONH          H.sup.+            47 H            CH.sub.2 CF.sub.3                                                                            CH.sub.3                                                                            H H  7-C.sub.6 H.sub.5                                                                              H.sup.+            48 5-COOCH.sub.3                                                                              CH.sub.2 C.sub.6 H.sub.5                                                                     CH.sub.3                                                                            H H  7-CH.sub.3 CONH  H.sup.+            49 H            CH.sub.2 C.sub.6 H.sub.5                                                                     CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.3 CONH  H.sup.+            50 H            C.sub.2 H.sub.5                                                                              CH(CH.sub.3).sub.2                                                                  H H  7-CH.sub.3       H.sup.+            51 CH.sub.2 CHC1CH.sub.2 Cl                                                                   CH.sub.2 CH.sub.2 OH                                                                         CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH(OH)CH(OH)CH.sub.2 OH                                                                      H.sup.+  52 CH.                                                               sub.2 CN C.sub.                                                               2 H.sub.5 CH.su                                                               b.3 CH.sub.3                                                                  CH.sub.3 7-CF.s                                                               ub.3 H.sup.+       53 CH.sub.2 CH.sub.2 OH                                                                       C.sub.4 H.sub.9 (n)                                                                          CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.2C.sub.6 H.sub.11                                                                     H.sup.+            54 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                         H              CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.2 OOCCH.sub.2 OCH.sub.3                                                               H.sup.+            55 CH.sub.2 OCPh                                                                              C.sub.6 H.sub.5                                                                              CH.sub.3                                                                            H H  7-CH.sub.2 COOCH.sub.                                                                          H.sup.+            56 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                      CH.sub.2 CH.sub.2 OH                                                                         CH.sub.3                                                                            H H  7-CH.sub.2 Ph    H.sup.+            57 CH.sub.2 OCCH.sub.3                                                                        CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.2 SO.sub.2 NHCH.sub.3                                                                 H.sup.+            58 CH.sub.2 OOCCH.sub.3                                                                       CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 (n)                                                       CH.sub.3                                                                            H H  7-CH.sub.2 CH.sub.2 SO.sub.2                                                  NH.sub.2         H.sup.+            59 CH.sub.2 CONH.sub.2                                                                        C.sub.2 H.sub.5                                                                              H     H H  7-CH.sub.2 CONHC.sub.2 H.sub.5                                                                 Na.sup.+           60 CH.sub.2 CONHC.sub.2 H.sub.5                                                               CH.sub.2 CH.sub.2 CONH.sub.2                                                                 CH.sub.3                                                                            H H  7-CH.sub.2 CONH.sub.2                                                                          Na.sup.+           61 CH.sub.2 CH.sub.2 SO.sub.2 NH.sub.2                                                        CH.sub.2 CH.sub.2 CONHC.sub.2 H.sub.5                                                        CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.2 OOCCH.sub.3                                                                         Na.sup.+           62 CH.sub.2 SO.sub.2 NHCH.sub.3                                                               C.sub.6 H.sub.11                                                                             CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.2 OCCH.sub.3                                                                          K.sup.+            63 CH.sub.2 Ph  CH.sub.2 CH.sub.2 OH                                                                         CH.sub.3                                                                            CH.sub. 3 CH.sub.3                                                                 7-CH.sub.2 CH.sub.2 OCH.sub.2                                                 CH.sub.2 OC.sub.2 H.sub.5                                                                      K.sup.+            64 CH.sub.2 COOCH.sub.3                                                                       CH.sub.2 OC.sub.6 H.sub.5                                                                    CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.2 OCPh  K.sup.+            65 CH.sub.2 OOCCH.sub.2 OCH.sub.3                                                             CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3                                                         CH.sub.3                                                                            CH.sub.3 CH.sub.3                                                                  7-CH.sub.2 CH.sub.2 OC.sub.2                                                  H.sub.5          K.sup.+            66 CH.sub.2C.sub.6 H.sub.11                                                                   CH.sub.2 COCH.sub.3                                                                          CH.sub.3                                                                            H H  7-CH.sub.2 CH.sub.2 OH                                                                         K.sup.+            67 CF.sub.3     CH.sub.2 CH.sub.2 Cl                                                                         CH.sub.3                                                                            H H  7-CH.sub.2 CN    NH.sub.4.sup.+     68 CH(OH)CH(OH)CH.sub.2 OH                                                                    (CH.sub.2).sub.3 OH                                                                          CH.sub.3                                                                            H H  7-CH.sub.2 CHClCH.sub.2                                                                        NH.sub.4.sup.+     __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________     ##STR5##                                                                     Number                                                                             R.sup.5       R               R.sup.1                                                                              R.sup.6   M                         __________________________________________________________________________    1    H             CH.sub.2 CH.sub.2 OH                                                                          CH.sub.3                                                                             CH.sub.3  H.sup.+                   2    H             C.sub.2 H.sub.5 CH.sub.3                                                                             CH.sub.3  H.sup.+                   3    H             C.sub.4 H.sub.9 (n)                                                                           CH.sub.3                                                                             CH.sub.3  H.sup.+                   4    5-SO.sub.3 H  H               CH.sub.3                                                                             CH.sub.3 CONH                                                                           H.sup.+                   5    H             C.sub.6 H.sub.5 CH.sub.3                                                                             CH.sub.3  H.sup.+                   6    5-CN          CH.sub.2 CH.sub.2 OH                                                                          CH.sub.3                                                                             OC.sub.2 H.sub.5                                                                        H.sup.+                   7    H             CH.sub.2 CH.sub.2 Cl                                                                          CH.sub.3                                                                             H         H.sup.+                   8    H             CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 (n)                                                        CH.sub.3                                                                             Cl        H.sup.+                   9    5-SC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5 H      CH.sub.3 CONH                                                                           Na.sup.+                  10   H             CH.sub.2 CH.sub.2 CONH.sub.2                                                                  CH.sub.3                                                                             CH.sub.3  Na.sup.+                  11   5-SO.sub.3 Na CH.sub.2 CH.sub.2 CONHC.sub.2 H.sub.5                                                         CH.sub.3                                                                             Br        Na.sup.+                  12   4-CN, 5-Cl    C.sub.6 H.sub.11                                                                              CH.sub.3                                                                             CH.sub.3  K.sup.+                   13   4,5-di-Cl6-CH.sub. 3                                                                        CH.sub.2 CH.sub.2 OH                                                                          CH.sub.3                                                                             CH.sub.3  K.sup.+                   14   H             CH.sub.2 OC.sub.6 H.sub.5                                                                     CH.sub.3                                                                             SCH.sub.3 K.sup.+                   15   5-SO.sub.2 CH.sub.3                                                                         CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2                                CH.sub.3        CH.sub.3                                                                             CH.sub.3 CONH                                                                           K.sup.+                   16   H             CH.sub.2 COCH.sub.3                                                                           CH.sub.3                                                                             CH.sub.3 CH.sub.2 CONH                                                                  K.sup.+                   17   6-SO.sub.2 NH.sub.2                                                                         CH.sub.2 CH.sub.2 Cl                                                                          CH.sub.3                                                                             CH.sub.3  NH.sub.4.sup.+            18   H             (CH.sub.2).sub.3 OH                                                                           CH.sub.3                                                                             OC.sub.6 H.sub.5                                                                        NH.sub.4.sup.+            19   5-SO.sub.3 HN(Et).sub.3                                                                     CH.sub.2 CONH.sub.2                                                                           CH.sub.3                                                                             C.sub.6 H.sub.5 CONH                                                                    N.sup.+ H(Et).sub.3       20   H             C.sub.2 H.sub.5 CH.sub.3                                                                             CH.sub.3 SO.sub.2 NH                                                                    N.sup.+ H(Et).sub.3       21   5-CONH.sub.2  CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                 CH.sub.3                                                                             CH.sub.3 CONH                                                                           NH.sub.4.sup.+            22   H             CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 (n)                                                        CH.sub.3                                                                             CH.sub.3 CONH                                                                           N.sup.+ H(Et).sub.3       23   H             C.sub.2 H.sub.5 CH.sub.3                                                                             HCONH     N.sup.+ H(Et).sub.3       24   5-Cl          CH.sub.2 CH.sub.2 COOCH.sub.3                                                                 CH.sub.3                                                                             CH.sub.3  N.sup.+ H(Et).sub.3       25   5-Cl          CH.sub.2 CH.sub.2 CONH.sub.2                                                                  CH.sub.3                                                                             CH.sub.3  N.sup.+ H(CH.sub.2                                                            CH.sub.2 OH).sub.3        26   5-Cl          CH.sub.2 CH.sub.2 CN                                                                          CH.sub.3                                                                             CH.sub.3  N.sup.+ H(CH.sub.2                                                            CH.sub.2 OH).sub.3        27   4-OOCCH.sub.3 C.sub.4 H.sub.9 (n)                                                                           CH.sub.3                                                                             CH.sub.3  N.sup.+ H(CH.sub.2                                                            CH.sub.2 OH).sub.3        28   5-CH.sub.2 CONHCH.sub.3                                                                     CH.sub.2 C.sub.6 H.sub.5                                                                      CH.sub.3                                                                             CH.sub.3  N.sup.+ H(CH.sub.2                                                            CH.sub.2 OH).sub.3        29   H             CH.sub.2 CONHCH.sub. 3                                                                        CH.sub.3                                                                             C.sub.6 H.sub.5 CH.sub.2                                                                N.sup.+ H.sub.2                                                               (CH.sub.2 CH.sub.2                                                            OH).sub.2                 30   5-Br          CH.sub.2 SO.sub.2 NHCH.sub.3                                                                  CH.sub.3                                                                             CH.sub.3  N.sup.+ H.sub.2                                                               (CH.sub.2 CH.sub.2                                                            OH).sub.2                 31   5-CH.sub.2 SO.sub.2 NHCH.sub.3                                                              (CH.sub.3).sub.2 CH                                                                           CH.sub.3                                                                             CH.sub.3  N.sup.+ H.sub.2                                                               (CH.sub.2 CH.sub.2                                                            OH).sub.2                 32   5-Br          (CH.sub.3).sub.2 CHCH.sub.2                                                                   CH.sub.3                                                                             CH.sub.3 CONH                                                                           N.sup.+ H.sub.2                                                               (CH.sub.2 CH.sub.2                                                            OH).sub.2                 33   4-NHCOCH.sub.3                                                                              CH.sub.2 CH.sub.2 CONH.sub.2                                                                  CH.sub.3                                                                             CH.sub.3  N.sup.+ H(CH.sub.3).su                                                        b.2 C.sub.6 H.sub.5       34   4,5,6-tri-Cl  C.sub.2 H.sub.5 CH.sub.3                                                                             CH.sub.3  N.sup.+ H(CH.sub.3).su                                                        b.2 C.sub.6 H.sub.5       35   H             CH.sub.2 CH.sub.2 SO.sub.2 NH.sub.2                                                           CH.sub.3                                                                             CH.sub.3 CH.sub.2 CONH                                                                  N.sup.+ H(CH.sub.3).su                                                        b.2 C.sub.6 H.sub.5       36   5-Me          CH.sub.2 OOCCH.sub.2 CH.sub.2 OCH.sub.3                                                       CH.sub.3                                                                             CH.sub.3  NH.sub.4.sup.+            37   5-Me          CH.sub.2 CH.sub.2 CONH.sub.2                                                                  CH.sub.3                                                                             CH.sub.2 CONH                                                                           NH.sub.4.sup.+            38   5-SO.sub.3 NH.sub.4                                                                         CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                            CH.sub.3                                                                             C.sub.6 H.sub.5                                                                         NH.sub.4.sup.+            39   4-MeO         CH.sub.2 C.sub.6 H.sub.11                                                                     CH.sub.3                                                                             CH.sub.3  NH.sub.4.sup.+            40   4-MeO         CH.sub.2 CH.sub.2 OH                                                                          CH.sub.3                                                                             CH.sub.3  H.sup.+                   41   4-MeO         CH(OH)CH.sub.2 CH.sub.2 OH                                                                    CH.sub.3                                                                             CH.sub.3 CONH                                                                           H.sup.+                   42   5-SO.sub.3 H  C.sub.2 H.sub.5 CH.sub.3                                                                             CH.sub.3  H.sup.+                   43   5-SO.sub.3 H  CH.sub.2 CH.sub.2 OH                                                                          CH.sub.3                                                                             OCH.sub.3 H.sup.+                   44   5-SO.sub.3 H  CH.sub.2 CH.sub.2 OH                                                                          CH.sub.3                                                                             H         H.sup.+                   45   5-NHSO.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub.2 Br                                                                          CH.sub.3                                                                             CH.sub.3 CH.sub.2 CONH                                                                  H.sup.+                   46   H             CH.sub.2 CH.sub.2 I                                                                           CH.sub.3                                                                             HCONH     H.sup.+                   47   H             CH.sub.2 CF.sub.3                                                                             CH.sub.3                                                                             C.sub.6 H.sub.5                                                                         H.sup.+                   48   5-COOCH.sub.3 CH.sub.2 C.sub.6 H.sub.5                                                                      CH.sub.3                                                                             CH.sub.3 CONH                                                                           H.sup.+                   49   H             CH.sub.2 C.sub.6 H.sub.5                                                                      CH.sub.3                                                                             CH.sub.3 CONH                                                                           H.sup.+                   50   H             C.sub. 2 H.sub.5                                                                              CH(CH.sub.3).sub.2                                                                   CH.sub.3  H.sup.+                   51   CH.sub.2 CHClCH.sub.2 Cl                                                                    CH.sub.2 CH.sub.2 OH                                                                          CH.sub.3                                                                             CH.sub.3  H.sup.+                   52   CH.sub.2 CN   C.sub.2 H.sub.5 CH.sub.3                                                                             CH.sub.3  H.sup.+                   53   CH.sub.2 CH.sub.2 OH                                                                        C.sub.4 H.sub.9 (n)                                                                           CH.sub.3                                                                             CH.sub.3  H.sup.+                   54   CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                          H               CH.sub.3                                                                             CH.sub.3  H.sup.+                   55   CH.sub.2 OCPh C.sub.6 H.sub.5 CH.sub.3                                                                             H         H.sup.+                   56   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                       CH.sub.2 CH.sub.2 OH                                                                          CH.sub.3                                                                             H         H.sup.+                   57   CH.sub.2 OCCH.sub.3                                                                         CH.sub.2 CH.sub.2 Cl                                                                          CH.sub.3                                                                             CH.sub.3  H.sup.+                   58   CH.sub.2 OOCCH.sub.3                                                                        CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 (n)                                                        CH.sub.3                                                                             H         H.sup.+                   59   CH.sub.2 CONH.sub.2                                                                         C.sub.2 H.sub.5 H      H         Na.sup.+                  60   CH.sub.2 CONHC.sub.2 H.sub.5                                                                CH.sub.2 CH.sub.2 CONH.sub.2                                                                  CH.sub.3                                                                             H         Na.sup.+                  61   CH.sub.2 CH.sub.2 SO.sub.2 NH.sub.2                                                         CH.sub.2 CH.sub. 2 CONHC.sub.2 H.sub.5                                                        CH.sub.3                                                                             CH.sub.3  Na.sup.+                  62   CH.sub.2 SO.sub.2 NHCH.sub.3                                                                C.sub.6 H.sub.11                                                                              CH.sub.3                                                                             CH.sub.3  K.sup.+                   63   CH.sub.2 Ph   CH.sub.2 CH.sub.2 OH                                                                          CH.sub.3                                                                             CH.sub.3  K.sup.+                   64   CH.sub.2 COOCH.sub.3                                                                        CH.sub.2 OC.sub.6 H.sub.5                                                                     CH.sub.3                                                                             CH.sub.3  K.sup.+                   65   CH.sub.2 OOCCH.sub.2 OCH.sub.3                                                              CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2                                CH.sub.3        CH.sub.3                                                                             CH.sub.3  K.sup.+                   66   CH.sub.2C.sub.6 H.sub.11                                                                    CH.sub.2 COCH.sub.3                                                                           CH.sub.3                                                                             H         K.sup.+                   67   CF.sub.3      CH.sub.2 CH.sub.2 Cl                                                                          CH.sub.3                                                                             H         NH.sub.4.sup.+            68   CH(OH)CH(OH)CH.sub.2 OH                                                                     (CH.sub.2).sub.3 OH                                                                           CH.sub.3                                                                             H         NH.sub.4.sup.+            0326B                                                                         __________________________________________________________________________

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:
 1. A dye according to the formula: ##STR6## wherein R⁵ is 0-3substituents independently selected from halogen, cyano, alkyl, alkoxy,alkylthio, alkylsulfonyl, sulfamoyl, alkylsulfamoyl, alkanoyloxy,carbamoyl, alkylcarbamoyl, alkoxycarbonyl, alkanoylamino, and SO₃ M; Mis selected from H⁺, NH₄ ⁺, Na⁺, K⁺, and the colorless cations of saltsof triethylamine, tri(2-hydroxyethyl)amine, di(2-hydroxyethyl)amine, orN,N-dimethylaniline; C is a coupler having the formula ##STR7## whereinR is selected from hydrogen, alkyl, aryl, and cycloalkyl; R¹, R², and R³are each selected from hydrogen and alkyl; R⁴ is 0-2 substituents and R⁶is 0 or 1 substituent selected from alkyl, alkoxy, halogen,alkanoylamino, alkylthio, and aryloxy; and wherein the alkyl moieties ofR, R⁴, R⁵ and R⁶ are unsubstituted or substituted with 1-3 substituentsindependently selected from halogen, CN, OH, alkoxy, aryloxy,alkoxyalkoxy, alkanoyl, alkanoyloxy, carbamoyl, alkylcarbamoyl,sulfamoyl, alkylsulfamoyl, aryl, alkoxycarbonyl, alkoxyalkanoyloxy, andcycloalkyl.
 2. The dye of claim 1 wherein R⁵ is 0-3 substituentsselected from Cl, Br, alkyl, alkoxy, and --SO₃ M; R is alkyl, or alkylsubstituted with 1-3 substituents independently selected from hydroxy,Cl, Br, alkoxy, carbamoyl, alkanoyloxy, alkoxycarbonyl, cyano, phenyl,and sulfamoyl; R¹, R² and R³ are each independently selected from H andalkyl; and R⁴ is 0-2 substituents independently selected from alkyl,alkoxy, alkylthio, phenyl, and alkanoylamino.
 3. The dye of claim 2wherein R⁵ is H or one of said substituents in the 4 or 5 position, andR⁴ is H or one of said substituents in the seven position.
 4. The dyeaccording to claim 1 of the formula ##STR8##
 5. The dye according to anyone of claims 1, 2 and 3 wherein the coupler has the formula ##STR9##wherein R, R¹, R², R³ and R⁴ are as defined therein.
 6. The dyeaccording to any one of claims 1, 2 and 3 wherein the coupler has theformula ##STR10## wherein R, R¹ and R⁶ are as defined therein.
 7. Thedye according to claim 1 of the formula ##STR11##
 8. The dye accordingto claim 1 of the formula ##STR12##
 9. The dye according to claim 1 ofthe formula ##STR13##
 10. The dye according to claim 1 of the formula##STR14##